CN109755656A - Novel " self-excitation live-in " lithium ion secondary reserve cell of one kind and preparation method thereof - Google Patents

Novel " self-excitation live-in " lithium ion secondary reserve cell of one kind and preparation method thereof Download PDF

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CN109755656A
CN109755656A CN201910031541.3A CN201910031541A CN109755656A CN 109755656 A CN109755656 A CN 109755656A CN 201910031541 A CN201910031541 A CN 201910031541A CN 109755656 A CN109755656 A CN 109755656A
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pole piece
lithium
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CN109755656B (en
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谢科予
沈超
侯倩
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Northwestern Polytechnical University
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention discloses a kind of novel " self-excitation live-in " lithium ion secondary reserve cells, are assembled by processed anode pole piece and cathode pole piece and processed diaphragm.The invention also discloses the preparation methods of above-mentioned reserve cell, comprising the following steps: S1, positive active material, negative electrode active material is prepared into slurry respectively, and is coated in collection liquid surface, drying, tabletting obtains anode pole piece and cathode pole piece;S2, thermo-responsive electrolyte solvent material and lithium salts are dissolved separately in organic solvent to get thermo-responsive electrolyte dispersion liquid and lithium salts dispersion liquid is arrived;S3, the surface that thermo-responsive electrolyte dispersion liquid and lithium salts dispersion liquid are respectively coated on to anode pole piece, cathode pole piece and diaphragm are dried to get processed anode pole piece, cathode pole piece and diaphragm is arrived;S4, it is assembled according to conventional batteries assemble method to get reserve cell is arrived.The self-discharge rate of battery is effectively reduced in the present invention, promotes battery storage life.

Description

Novel " self-excitation live-in " lithium ion secondary reserve cell of one kind and preparation method thereof
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of novel " self-excitation live-in " lithium ion secondary reserve Battery and preparation method thereof.
Background technique
With the extensive use of movement/fixation military reserve power supply, Weapons Power system, emergency power supply, for reserve Battery it is secondary can the requirements of the performances such as charge-discharge characteristic, reliability be continuously improved.It is limited to design feature simultaneously, meets high power It is required that lithium ion reserve cell can not obtain lower self-discharge rate etc..Therefore, tradition reserve lithium battery cannot be considered in terms of Gao Gong The requirement of rate characteristic and long-term memory reliability, it is fast that this has become restriction reserve power supply, Weapons Power system, emergency power system One urgent problem to be solved of speed development.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of novel " self-excitation live-in " lithium ions two Secondary reserve cell and preparation method thereof, with meet reserve cell can charge and discharge, high power and long term storage are stable the needs of.
The first purpose of the invention is to provide a kind of novel " self-excitation live-in " lithium ion secondary reserve cells, by through overheating The processed anode pole piece of sensitive electrolyte dispersion liquid and cathode pole piece and by the processed diaphragm assembling of lithium salts dispersion liquid It forms.
Preferably, thermo-responsive electrolyte dispersion liquid is dissolved in organic solvent for thermo-responsive electrolyte solvent material and disperses It arrives.
Preferably, thermo-responsive electrolyte solvent material be trifluoromethane sulfonic acid inferior amine salt, dintrile amine salt, hexafluorophosphate, Tetrafluoroborate, N, N- diethyl-N- methyl-N- (n-propyl) ammonium trifluoromethyl trifluoroborate (N1223[CF3BF3]), fourth two One of nitrile, phthalonitrile or more than one combinations.
Preferably, lithium salts dispersion liquid is dissolved in dispersion in organic solvent for lithium salts and obtains.
Preferably, lithium salts is lithium perchlorate (LiClO4), LiBF4 (LiBF4), lithium hexafluoro phosphate (LiPF6), nitric acid Lithium (LiNO3), two (trimethyl fluoride sulfonyl) imine lithium (LiN (CF3SO2)2), dioxalic acid lithium borate (C4BLiO8), difluoro oxalate boron Sour lithium (LiBF2C2O4), trifluoromethanesulfonic acid lithium (LiCF3SO3), one of dicyanamide lithium (LiDCA) or more than one combinations.
Preferably, organic solvent is propene carbonate, ethylene carbonate, tetrahydrofuran, 1,2 dimethoxy-ethanes, 1,3- One of dioxolanes, acetonitrile or more than one combinations.
Preferably, organic solvent is tetrahydrofuran.
A second object of the present invention is to provide a kind of systems of above-mentioned novel " self-excitation live-in " lithium ion secondary reserve cell Preparation Method, comprising the following steps:
S1, positive active material, negative electrode active material are uniformly mixed with corresponding binder, conductive additive respectively, It is prepared into slurry, and even application, in collection liquid surface, drying obtains anode pole piece and cathode pole piece;
S2, thermo-responsive electrolyte solvent material and lithium salts are dissolved separately in organic solvent, and are uniformly dispersed to get arriving Thermo-responsive electrolyte dispersion liquid and lithium salts dispersion liquid;
S3, thermo-responsive electrolyte dispersion liquid obtained in S2 is respectively coated on anode pole piece obtained in S1 and cathode pole The surface of piece, and by lithium salts dispersion obtained in S2 on the surface of diaphragm, drying, tabletting to get to it is processed just Pole pole piece, cathode pole piece and diaphragm;
S4, by processed anode pole piece, cathode pole piece and diaphragm obtained in S3, according to conventional batteries assemble method into Row assembles to arrive novel " self-excitation live-in " the lithium ion secondary reserve cell;
Wherein, step S2, the operating process of S3 and S4 carries out under the conditions of dew point is less than -30 DEG C hydrophobic.
Preferably, in step S1, positive active material is LiFePO4, cobalt acid lithium, LiMn2O4, lithium nickelate, nickel cobalt aluminium three One of member, nickel-cobalt-manganese ternary, negative electrode active material are one of carbon material, silicon materials, lithium titanate.
Preferably, in step S2, the concentration of the thermo-responsive electrolyte dispersion liquid and lithium salts dispersion liquid is respectively 0.05- 1.0g/mL and 0.01-0.50g/mL.
Compared with prior art, the present invention the beneficial effect is that:
Novel " self-excitation live-in " lithium ion secondary reserve cell provided by the invention, based on the lithium-ion electric that can fill mode On the basis of pond body system, phase transition occurs in battery storage and working condition using thermo-responsive organic solvent and causes ionic conductivity Variation, and then realize the low self-discharge rate of static storage process, the high power characteristic of battery under operating condition.Particular by Thermo-responsive electrolyte solvent material and electrolyte lithium salt are respectively coated on positive and negative anodes and membrane surface, and are assembled into battery, Under the conditions of room temperature static storage, solvent, lithium salts are in solid-state, and the two solid-state properties keep its immiscible, the ion of battery is caused to be led Electrically extremely low, internal resistance is larger, and battery is not turned on, so that the self-discharge rate of battery reduces, is obviously improved the storage life of battery.And In high power work state, the spontaneous heat production at electrode interface by external impressed current causes phase transformation, temperature-sensitive by the big internal resistance of battery Sense electrolyte solvent melting diffusion mixes with lithium salts, and inside battery ion is connected at this time, and the ionic conductivity of battery can be promoted To 10-3The order of magnitude, excitation battery work, to meet the work requirements of battery.Terminate when battery works, be placed under low temperature and save, The ionic conductivity of battery is 10 at this time-5The order of magnitude can significantly reduce the self-discharge rate of secondary cell.Reserve provided by the invention Battery has the advantages that structure is simple and excitation is convenient controllable, effectively reduces the self-discharge rate of secondary reserve cell, improves The storage life of battery.
Detailed description of the invention
Fig. 1 is that electrochemistry of the lithium ion secondary reserve cell that provides of the embodiment of the present invention 2 under 0.1C current density is followed Ring performance map and coulombic efficiency figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, right with reference to the accompanying drawings and embodiments The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.The test method of actual conditions is not specified in the following example, usually according to normal condition, or presses According to condition proposed by each manufacturer.
The operating process of step S2, S3 and S4 carry out under the conditions of dew point is less than -30 DEG C hydrophobic in following embodiment.
Embodiment 1
A kind of preparation method of novel " self-excitation live-in " lithium ion secondary reserve cell, specifically includes the following steps:
S1,160mg LiFePO4 and 160mg graphite are uniformly mixed with 20mgPVDF, 20mg conductive black respectively, are prepared Even applications are distinguished on the surface of aluminium foil and copper foil with 250 μm of height faces of scraper at slurry, and by slurry, and drying obtains phosphoric acid Iron lithium anode pole piece and graphite cathode pole piece;
S2, by the LiClO of the phthalonitrile of 0.5g and 0.1g4It is dissolved separately in the tetrahydrofuran of 10ml, then magnetic Power is dispersed with stirring uniformly to get to phthalonitrile dispersion liquid and LiClO4Dispersion liquid;
S3, phthalonitrile dispersion liquid obtained in S2 is respectively coated on obtained in S1 with 100 μm of height faces of scraper One side surface of iron phosphate lithium positive pole pole piece and graphite cathode pole piece, and by LiClO obtained in S24Dispersion liquid is with 100 μ of scraper M height face is coated in the positive and negative surface of diaphragm, and 12h is then respectively dried under the conditions of 40 DEG C, then strikes out anode pole piece Diameter is the pole piece of 12mm, and cathode pole piece is struck out the pole piece that diameter is 15mm, diaphragm is stamped into the specification of diameter 19mm, Processed anode pole piece, cathode pole piece and diaphragm are arrived to obtain the final product;
S4, by processed anode pole piece, cathode pole piece and diaphragm obtained in S3, according to conventional button cell assembling side Method is assembled to arrive novel " self-excitation live-in " the lithium ion secondary reserve cell.
Embodiment 2
A kind of preparation method of novel " self-excitation live-in " lithium ion secondary reserve cell, specifically includes the following steps:
S1,160mg cobalt acid lithium and 160mg graphite are uniformly mixed with 20mgPVDF, 20mg conductive black respectively, are prepared into Slurry, and slurry is distinguished into even applications on the surface of aluminium foil and copper foil with 250 μm of height faces of scraper, drying obtains cobalt acid lithium Anode pole piece and graphite cathode pole piece;
S2, the N by 10g1223[CF3BF3] and 5g LiN (CF3SO2)2It is dissolved separately in the tetrahydrofuran of 100ml, so Magnetic agitation is uniformly dispersed to get N is arrived afterwards1223[CF3BF3] dispersion liquid and LiN (CF3SO2)2Dispersion liquid;
S3, by N obtained in 20mL S21223[CF3BF3] dispersion liquid is fitted into flush coater, against the acid of cobalt obtained in S1 One side surface of lithium anode pole piece, is sprayed with given pace, is finished until dispersion liquid sprays, then will obtain in 20mL S2 N1223[CF3BF3] dispersion liquid is fitted into flush coater, against a side surface of graphite cathode pole piece obtained in S1, with a constant speed Rate is sprayed, until dispersion liquid spraying finishes, and by LiN (CF obtained in 20mL S23SO2)2Dispersion liquid is packed into flush coater In, against side length be 8cm diaphragm, with given pace spray diaphragm two sides, until dispersion liquid spraying finish, after spraying in 12h is respectively dried under the conditions of 40 DEG C, anode pole piece is then struck out into the pole piece that diameter is 12mm, cathode pole piece is struck out directly Diameter be 15mm pole piece, by diaphragm be stamped into the specification of diameter 19mm to get to processed anode pole piece, cathode pole piece and every Film;
S4, by processed anode pole piece, cathode pole piece and diaphragm obtained in S3, according to conventional button cell assembling side Method is assembled to arrive novel " self-excitation live-in " the lithium ion secondary reserve cell.
Embodiment 3
A kind of preparation method of novel " self-excitation live-in " lithium ion secondary reserve cell, specifically includes the following steps:
S1,160mg nickel cobalt aluminium tertiary cathode material and 160mg graphite are mixed with 20mgPVDF, 20mg conductive black respectively It closes uniformly, is prepared into slurry, and slurry is distinguished into even applications on the surface of aluminium foil and copper foil with 250 μm of height faces of scraper, dries It is dry, obtain nickel cobalt aluminium tertiary cathode pole piece and graphite cathode pole piece;
S2, by the LiCF of the phthalonitrile of 5g and 1g3SO3It is dissolved separately in the tetrahydrofuran of 10ml, then magnetic force stirs It mixes and is uniformly dispersed to get phthalonitrile dispersion liquid and LiCF is arrived3SO3Dispersion liquid;
S3, phthalonitrile dispersion liquid obtained in S2 is respectively coated on obtained in S1 with 100 μm of height faces of scraper One side surface of nickel cobalt aluminium tertiary cathode pole piece and graphite cathode pole piece, and by LiCF obtained in S23SO3Dispersion liquid is with scraper 100 μm of height faces are coated in the positive and negative surface of diaphragm, and 12h is then respectively dried under the conditions of 40 DEG C, then rushes anode pole piece It is pressed into the pole piece that diameter is 12mm, cathode pole piece is struck out into the pole piece that diameter is 15mm, diaphragm is stamped into diameter 19mm's Specification to get arrive processed anode pole piece, cathode pole piece and diaphragm;
S4, by processed anode pole piece, cathode pole piece and diaphragm obtained in S3, according to conventional button cell assembling side Method is assembled to arrive novel " self-excitation live-in " the lithium ion secondary reserve cell.
Embodiment 4
A kind of preparation method of novel " self-excitation live-in " lithium ion secondary reserve cell, specifically includes the following steps:
S1,160mg nickel-cobalt-manganternary ternary anode material and 160mg silicon-carbon cathode material are led with 20mgPVDF, 20mg respectively Electric carbon black is uniformly mixed, and is prepared into slurry, and by slurry with 250 μm of height faces difference even applications of scraper in aluminium foil and copper foil Surface, drying, obtains nickel-cobalt-manganese ternary anode pole piece and silicon-carbon cathode pole piece;
S2, the N by 10g1223[CF3BF3] and 5g LiBF2C2O4It is dissolved separately in the tetrahydrofuran of 10ml, then magnetic Power is dispersed with stirring uniformly to get to N1223[CF3BF3] dispersion liquid and LiBF2C2O4Dispersion liquid;
S3, by N obtained in S21223[CF3BF3] dispersion liquid is respectively coated on obtained in S1 with 100 μm of height faces of scraper One side surface of nickel-cobalt-manganese ternary anode pole piece and silicon-carbon cathode pole piece, and by LiBF obtained in S22C2O4Dispersion liquid is with scraper 100 μm of height faces are coated in the positive and negative surface of diaphragm, and 12h is then respectively dried under the conditions of 40 DEG C, then rushes anode pole piece It is pressed into the pole piece that diameter is 12mm, cathode pole piece is struck out into the pole piece that diameter is 15mm, diaphragm is stamped into diameter 19mm's Specification to get arrive processed anode pole piece, cathode pole piece and diaphragm;
S4, by processed anode pole piece, cathode pole piece and diaphragm obtained in S3, according to conventional button cell assembling side Method is assembled to arrive novel " self-excitation live-in " the lithium ion secondary reserve cell.
We electrical property to the novel electrolytes in the reserve cell of preparation and prepared obtain by taking embodiment 2 as an example The electrochemistry of reserve cell can be carried out research
One, electro-chemical test is carried out to the electrolyte in the reserve cell of preparation
The N that will be prepared in embodiment 21223[CF3BF3] dispersion liquid and LiN (CF3SO2)2Dispersion liquid is uniformly mixed, and is added dropwise to Membrane surface obtains electrolyte sheet after being dried under vacuum to solvent volatilization, and the clean stainless steel of electrolyte sheet and two panels is blocked electricity Pole piece is assembled into SS//SS Symmetrical cells, and in -20-150 DEG C of progress testing impedances, is calculated not by following formula (1) The ionic conductivity of synthermal lower electrolyte, as shown in table 1.
σ=L/RS (1)
Wherein, L is Electrolyte film thickness, and S is the contact area of blocking electrode and electrolyte sheet, and R is the body electricity of electrolyte Resistance.
1 ionic conductivity of table-thermometer
Table 1 is ionic conductivity table of the electrolyte sheet of the preparation of embodiment 2 under different temperatures, it can be seen from Table 1 that, At 20 DEG C of room temperature, the ionic conductivity of electrolyte is 5.34mS/cm, 10-3The order of magnitude, when (- 20 DEG C) are protected under low temperature When depositing, the ionic conductivity of electrolyte is 0.080mS/cm, is significantly reduced to 10-5The order of magnitude.
Two, the self-activation parameter of the reserve cell of preparation is tested
The button full battery of preparation is subjected to self-activation according to the square experiment of design, and electrochemical impedance is combined to test ratio The impedance magnitude of battery less under coactivation mode, so that it is determined that best activation parameter, as shown in table 2.
2 self-activation parameter list of table
It can be seen from Table 2 that temperature is affected to self-activation effect, as temperature is increased to 100 DEG C, when activation Between significantly reduce to 3h, current density is down to 1mA/cm2, it is thus determined that being best activation parameter.
Three, test can be carried out to the electrochemistry of the reserve cell of preparation
Button full battery prepared by embodiment 2 is activated under best activation parameter, and at room temperature, at 0.1C times Cycle performance of battery test is carried out under rate.
Fig. 1 is the cycle performance figure and coulombic efficiency figure of full battery.From figure 1 it appears that under 0.1C multiplying power, battery Discharge capacity be up to 160mAh/g, 40 circle of circulation can be stablized, and its coulombic efficiency maintains essentially in 100%, this shows that this is new Type structure reserve cell has preferable secondary stable charge/discharge.
Four, self-discharge rate test is carried out to the reserve cell of preparation
It in embodiment 2 after activated batteries work, places it in room temperature and is placed, by testing different storage times Under open-circuit voltage, select precision be 0.1mV instrument test self discharge, according to the following formula (2) calculate K value to assessment from The size of discharge rate, as shown in table 3.
K=- (OCV2-OCV1)/T (2)
Wherein, OCV1For initial voltage, OCV2For final voltage, T is temperature.
The OCV of 2 battery of the embodiment of the present invention1=4.0605V, remains unchanged, only OCV2It, can be according to OCV for variable2 Value determines the size of self discharge K value, i.e., only need to examine a full battery voltage after self discharge test.
Table is tested in 3 self discharge of table
It can be seen from Table 3 that voltage drop absolute value increases as storage time is elongated, instrument test can be reduced simultaneously When absolute error so that test result is more acurrate.By being up to test in 190 days, K value is maintained at the left side 0.87mV/d The right side, far smaller than 2mV/d illustrate that reserve cell prepared by the present invention has low-down self-discharge rate.
In conclusion reserve cell prepared by the present invention, before activation, ion is not turned on characteristic and significantly reduces electricity battery The self discharge in pond improves the storage life of battery.And then by optimization self-activation parametric excitation battery work, and study its electricity Chemical property, having obtained one kind can charge and discharge, stable secondary deposit self-activation battery.Terminate when battery works, is placed in low temperature Lower preservation, the significant decrease of battery ions conductivity effectively reduce the self-discharge rate of secondary reserve cell, improve battery Storage life.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies Within, then the present invention is also intended to include these modifications and variations.

Claims (10)

1. a kind of novel " self-excitation live-in " lithium ion secondary reserve cell, which is characterized in that by dispersing by thermo-responsive electrolyte The processed anode pole piece of liquid and cathode pole piece and the process processed diaphragm of lithium salts dispersion liquid assemble.
2. novel " self-excitation live-in " lithium ion secondary reserve cell according to claim 1, which is characterized in that the temperature-sensitive Sense electrolyte dispersion liquid is dissolved in dispersion in organic solvent for thermo-responsive electrolyte solvent material and obtains.
3. novel " self-excitation live-in " lithium ion secondary reserve cell according to claim 2, which is characterized in that the temperature-sensitive Sense electrolyte solvent material is trifluoromethane sulfonic acid inferior amine salt, dintrile amine salt, hexafluorophosphate, tetrafluoroborate, N, N- diethyl One of base-N- methyl-N- (n-propyl) ammonium trifluoromethyl trifluoroborate, succinonitrile, phthalonitrile or more than one Combination.
4. novel " self-excitation live-in " lithium ion secondary reserve cell according to claim 1, which is characterized in that the lithium salts Dispersion liquid is dissolved in dispersion in organic solvent for lithium salts and obtains.
5. novel " self-excitation live-in " lithium ion secondary reserve cell according to claim 4, which is characterized in that the lithium salts For lithium perchlorate, LiBF4, lithium hexafluoro phosphate, lithium nitrate, two (trimethyl fluoride sulfonyl) imine lithiums, dioxalic acid lithium borate, One of difluorine oxalic acid boracic acid lithium, trifluoromethanesulfonic acid lithium, dicyanamide lithium or more than one combinations.
6. novel " self-excitation live-in " lithium ion secondary reserve cell according to claim 2 or 4, which is characterized in that described Organic solvent is propene carbonate, in ethylene carbonate, tetrahydrofuran, 1,2 dimethoxy-ethanes, 1,3- dioxolanes, acetonitrile One or more kinds of combinations.
7. novel " self-excitation live-in " lithium ion secondary reserve cell according to claim 6, which is characterized in that described organic Solvent is tetrahydrofuran.
8. a kind of preparation side of novel " self-excitation live-in " lithium ion secondary reserve cell according to claim 1-7 Method, which comprises the following steps:
S1, positive active material, negative electrode active material are uniformly mixed with corresponding binder, conductive additive respectively, are prepared At slurry, and even application, in collection liquid surface, drying obtains anode pole piece and cathode pole piece;
S2, thermo-responsive electrolyte solvent material and lithium salts are dissolved separately in organic solvent, and are uniformly dispersed to get temperature-sensitive is arrived Feel electrolyte dispersion liquid and lithium salts dispersion liquid;
S3, thermo-responsive electrolyte dispersion liquid obtained in S2 is respectively coated on anode pole piece and cathode pole piece obtained in S1 Surface, and by lithium salts dispersion obtained in S2 on the surface of diaphragm, drying, tabletting is to get to processed positive pole Piece, cathode pole piece and diaphragm;
S4, by processed anode pole piece, cathode pole piece and diaphragm obtained in S3, carry out group according to conventional batteries assemble method It fills to get novel " self-excitation live-in " the lithium ion secondary reserve cell is arrived;
Wherein, step S2, the operating process of S3 and S4 carries out under the conditions of dew point is less than -30 DEG C hydrophobic.
9. the preparation method of novel " self-excitation live-in " lithium ion secondary reserve cell according to claim 8, feature exist In in step S1, the positive active material is LiFePO4, cobalt acid lithium, LiMn2O4, lithium nickelate, nickel cobalt aluminium ternary, nickel cobalt manganese One of ternary, the negative electrode active material are one of carbon material, silicon materials, lithium titanate.
10. the preparation method of novel " self-excitation live-in " lithium ion secondary reserve cell according to claim 8, feature exist In in step S2, the concentration of the thermo-responsive electrolyte dispersion liquid and lithium salts dispersion liquid is respectively 0.05-1.0g/mL and 0.01- 0.50g/mL。
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CN107845847A (en) * 2016-09-20 2018-03-27 中国科学院大连化学物理研究所 A kind of lithium-sulfur cell with automatic control temperature function
CN107240705A (en) * 2017-05-10 2017-10-10 上海交通大学 A kind of middle temperature melting proton conductor dielectric film and its production and use
CN108493440A (en) * 2018-01-30 2018-09-04 中国科学院上海微系统与信息技术研究所 The positive electrode and preparation method thereof of molybdic acid lithium anode material of High Temperature Lithium Cell and preparation method thereof and High Temperature Lithium Cell
CN207910005U (en) * 2018-02-09 2018-09-25 王云燕 A kind of self-closing diaphragm cell of novel activation type
CN108808080A (en) * 2018-08-03 2018-11-13 南京博驰新能源股份有限公司 Nano-composite gel electrolyte, lithium secondary battery and preparation method thereof

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CN111092260A (en) * 2019-12-10 2020-05-01 浙江工业大学 Solid-like battery preparation method
CN111092260B (en) * 2019-12-10 2021-03-05 浙江工业大学 Solid-like battery preparation method
CN112018404A (en) * 2020-08-31 2020-12-01 中国人民大学 Temperature control battery for fire response and preparation method and application thereof
CN112018404B (en) * 2020-08-31 2022-02-11 中国人民大学 Temperature control battery for fire response and preparation method and application thereof

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